Supporting Information for Photo-deactivation pathways of ... · 1 Supporting Information for ... 1...

1

Supporting Information for

Photo-deactivation pathways of a double H-bonded photochromic Schiff base

investigated by combined theoretical calculations and experimental time-resolved

studies

Carlos Randino[a]

, Marcin Ziółek [b]

, Ricard Gelabert[a]

, Juan Angel Organero[b]

, Michal Gil[b]

,

Miquel Moreno*[a]

, José M. Lluch[a]

and Abderrazzak Douhal*[b]

Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona

(Spain) and Departamento de Química Física, Facultad de Ciencias Ambientales y

Bioquimicas, and INAMOL, Universidad de Castilla-La Mancha, Avda. Carlos III S.N. 45071

Toledo (Spain).

[a] Universitat Autònoma de Barcelona.

[b] Universidad de Castilla-La Mancha

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2011

2

Index:

Geometries and energies of the structures.

Stationary absorption spectrum of BSP in dichloromethane (Figure S1).

Time constants and their fractional amplitudes for BSP in hexane and dichloromethane

(Tables S1 and S2).

Femtosecond emission transients of BSP in hexane and dichloromethane (Figures S2

and S3).

Temporal changes in the absorbance spectrum of BSP in hexane (Figure S4).


3

Geometries and Energies of the Structures

In what follows the geometries of the structures discussed in the paper are presented. Each

geometry is presented framed in a table as a list of lines, each specifying the atomic number

and the (x,y,z)-coordinates in Ångstrom. We note that the atom sequence is not the same in

each structure, but the order in which the corresponding program selected to present the

structure.

Each table has a heading identifying the chemical structure by the abbreviation given in the

text, and the program under which it renders this energy (GAUSSIAN or TURBOMOLE). As

usual, an asterisk denotes a structure in the excited state. At the bottom, the absolute energy

obtained is reproduced to 8 decimal figures.

When a single structure is given and two energies are reported this means:

1. If it is a CI candidate, the reported TDDFT energies of ground and excited states at

that point, which ideally should be equal.

2. Otherwise, the structure has been optimized in the ground state with the program

indicated in the header of the Table, and a point calculation has been done for the

excited state (that is, this is a Franck-Condon excitation).

Energies in the paper for the ground state use as energy origin the minimum in S0 obtained

with Gaussian03. The energies appearing in the paper for the excited state structures are

computed with Turbomole, using as energy origin the minimum in S0 obtained with

Turbomole to have a coherent set of data.


4

Stable Structures (Ground State):

E

Optimized GAUSSIAN

MK

Optimized GAUSSIAN

6 7.035922 0.864888 -0.419105

6 5.637698 0.745952 -0.387905

6 5.045147 -0.348616 0.305044

6 5.883186 -1.283625 0.946158

6 7.262362 -1.158365 0.910169

6 7.831761 -0.075609 0.221039

1 7.466464 1.705326 -0.952873

1 5.422965 -2.115556 1.474161

1 7.894450 -1.886552 1.407173

1 8.912210 0.031894 0.186448

8 4.898355 1.671884 -1.012558

1 3.941790 1.424287 -0.875704

6 3.607871 -0.510602 0.359938

7 2.796848 0.326404 -0.203313

1 3.233117 -1.377176 0.919579

6 1.406636 0.126319 -0.190679

6 0.582627 1.263662 -0.220638

6 -0.800675 1.143744 -0.211057

6 -1.406654 -0.126035 -0.190636

6 -0.582602 -1.263396 -0.220811

6 0.800665 -1.143485 -0.211268

1 1.050560 2.242543 -0.250233

1 -1.415361 2.036913 -0.261184

1 -1.050593 -2.242248 -0.250546

1 1.415374 -2.036626 -0.261574

7 -2.796825 -0.326189 -0.203238

6 -3.607949 0.510699 0.360074

6 -5.045189 0.348622 0.305025

6 -5.883376 1.283550 0.946081

6 -7.262526 1.158104 0.910068

6 -7.831778 0.075230 0.220991

6 -7.035803 -0.865179 -0.419102

6 -5.637592 -0.746034 -0.387915

1 -5.423278 2.115573 1.474046

1 -7.894721 1.886224 1.407037

1 -8.912214 -0.032413 0.186405

1 -7.466207 -1.705709 -0.952837

1 -3.233266 1.377277 0.919754

8 -4.898134 -1.671883 -1.012559

1 -3.941593 -1.424217 -0.875688

6 -6.928077 1.221692 0.109977

6 -5.508018 0.964739 0.107522

6 -5.105934 -0.436031 -0.083041

6 -6.095148 -1.454086 -0.247208

6 -7.428639 -1.149265 -0.235008

6 -7.834443 0.208243 -0.053971

1 -7.239770 2.251788 0.248227

1 -5.764396 -2.481826 -0.384153

1 -8.176843 -1.924532 -0.360997

1 -8.897231 0.438275 -0.046432

8 -4.656995 1.890450 0.261684

6 -3.748311 -0.767292 -0.098870

7 -2.797753 0.154129 0.054561

1 -3.446130 -1.803583 -0.232403

6 -1.407417 -0.017071 0.046526

6 -0.614386 1.090164 0.388564

6 0.770283 0.992718 0.400976

6 1.406824 -0.216151 0.067115

6 0.605510 -1.326291 -0.248428

6 -0.778870 -1.231057 -0.275417

1 -1.096621 2.023802 0.662926

1 1.359664 1.851275 0.706122

1 1.093054 -2.263846 -0.495217

1 -1.360952 -2.103063 -0.552662

7 2.799180 -0.393629 0.068880

6 3.607433 0.577444 -0.215567

6 5.045274 0.427479 -0.159206

6 5.878671 1.515999 -0.489258

6 7.258648 1.405722 -0.444191

6 7.833771 0.182573 -0.063487

6 7.042945 -0.910112 0.265541

6 5.643799 -0.807389 0.223451

1 5.413895 2.454687 -0.781602

1 7.887274 2.252128 -0.699442

1 8.915061 0.085517 -0.025098

1 7.478300 -1.859014 0.559832

1 3.229311 1.558911 -0.528952

8 4.909139 -1.880588 0.544309

1 3.951583 -1.618843 0.451428

1 -3.236825 1.103748 0.190281

E(S0)

-1031.75257505 Eh

E(S0)

-1031.74456498 Eh


5

DK

Optimized GAUSSIAN

ER

Optimized GAUSSIAN

6 6.952356 1.153466 -0.003544

6 5.527245 0.928986 -0.003703

6 5.094043 -0.475422 0.002231

6 6.060960 -1.527749 0.007285

6 7.400944 -1.252699 0.006885

6 7.836526 0.107631 0.001421

1 7.286363 2.185807 -0.007616

1 5.707965 -2.557195 0.011481

1 8.132229 -2.053871 0.010624

1 8.904267 0.313297 0.001277

8 4.695964 1.885603 -0.008074

6 3.729109 -0.774820 0.003213

7 2.801551 0.182837 -0.001376

1 3.403318 -1.812598 0.008046

6 1.408416 0.051508 -0.001456

6 0.644402 1.230219 -0.001546

6 -0.742210 1.184247 -0.001635

6 -1.408424 -0.051505 -0.001418

6 -0.644409 -1.230215 -0.001746

6 0.742204 -1.184244 -0.001868

1 1.151226 2.190494 -0.001585

1 -1.294772 2.117020 -0.002274

1 -1.151234 -2.190490 -0.001943

1 1.294764 -2.117016 -0.002687

7 -2.801557 -0.182833 -0.001319

6 -3.729111 0.774827 0.003360

6 -5.094045 0.475426 0.002460

6 -6.060969 1.527747 0.007277

6 -7.400952 1.252687 0.006776

6 -7.836522 -0.107646 0.001339

6 -6.952343 -1.153475 -0.003322

6 -5.527236 -0.928984 -0.002987

1 -5.707982 2.557196 0.011303

1 -8.132243 2.053854 0.010286

1 -8.904262 -0.313320 0.001004

1 -7.286341 -2.185819 -0.007381

1 -3.403321 1.812606 0.008151

8 -4.695941 -1.885591 -0.007447

1 3.267769 1.131068 -0.004802

1 -3.267786 -1.131068 -0.004988

6 6.198565 0.704171 1.054777

6 4.854131 0.321923 0.926041

6 4.278003 0.221977 -0.372743

6 5.076076 0.514988 -1.497237

6 6.402385 0.891310 -1.360912

6 6.957005 0.982778 -0.074351

1 6.618031 0.773352 2.052713

1 4.627830 0.437633 -2.485053

1 7.004751 1.112390 -2.235605

1 7.996091 1.276836 0.043903

8 4.149131 0.062684 2.035184

1 3.227140 -0.183766 1.746039

6 2.897067 -0.173643 -0.551372

7 2.120904 -0.444630 0.448326

1 2.529964 -0.220705 -1.584677

6 0.801975 -0.886841 0.252991

6 -0.155258 -0.548672 1.224768

6 -1.479476 -0.941932 1.092770

6 -1.887058 -1.723700 -0.008017

6 -0.913982 -2.118937 -0.946673

6 0.404074 -1.690246 -0.830013

1 0.158578 0.045854 2.076905

1 -2.208595 -0.665387 1.846902

1 -1.211455 -2.775188 -1.758350

1 1.139631 -2.024031 -1.555182

7 -3.184274 -2.245119 -0.121508

6 -4.261624 -1.553593 -0.057219

6 -4.537061 -0.098574 -0.016021

6 -5.702958 0.279716 0.684201

6 -6.114950 1.600011 0.780961

6 -5.369947 2.590780 0.130737

6 -4.237638 2.250717 -0.596085

6 -3.809967 0.917553 -0.684273

1 -6.282932 -0.502009 1.168622

1 -7.007456 1.856629 1.341912

1 -5.679755 3.630383 0.183080

1 -3.656542 3.000277 -1.122608

1 -5.177390 -2.152796 -0.017626

8 -2.733295 0.706869 -1.479992

1 -2.357160 -0.176381 -1.344228

E(S0)

-1031.73607915 Eh

E(S0)

-1031.72711410 Eh


6

MKR1

Optimized GAUSSIAN

MKR2

Optimized GAUSSIAN

6 5.975409 -1.527579 -0.702757

6 4.641668 -0.979090 -0.651347

6 4.427038 0.106319 0.315906

6 5.502086 0.560490 1.140335

6 6.746866 0.000856 1.046496

6 6.970913 -1.053829 0.109756

1 6.148856 -2.329441 -1.412900

1 5.309771 1.365487 1.847046

1 7.561061 0.348802 1.673187

1 7.964584 -1.490647 0.044035

8 3.709175 -1.407723 -1.394300

6 3.161878 0.689962 0.426800

7 2.135588 0.290447 -0.323346

1 2.996294 1.488765 1.146270

6 0.822599 0.778523 -0.338593

6 -0.110954 0.107678 -1.146154

6 -1.431901 0.527375 -1.204919

6 -1.864711 1.643449 -0.460487

6 -0.913444 2.334773 0.315201

6 0.404549 1.900495 0.393819

1 0.210324 -0.753108 -1.725297

1 -2.138535 0.000926 -1.837247

1 -1.229590 3.222797 0.852863

1 1.104607 2.459354 1.005121

7 -3.155408 2.179409 -0.573280

6 -4.245273 1.510698 -0.473568

6 -4.554658 0.119840 -0.070835

6 -5.697074 -0.449671 -0.674053

6 -6.135157 -1.729619 -0.371030

6 -5.443412 -2.471441 0.593888

6 -4.337405 -1.929253 1.233224

6 -3.883707 -0.639748 0.919089

1 -6.235746 0.144294 -1.408278

1 -7.007376 -2.142568 -0.866705

1 -5.774886 -3.472068 0.855135

1 -3.798610 -2.479413 1.997246

1 -5.142886 2.075955 -0.745264

8 -2.838370 -0.197084 1.660022

1 -2.447983 0.604064 1.279775

1 2.440542 -0.495112 -0.958999

6 7.401811 0.832312 0.251579

6 5.966866 1.116308 0.278123

6 5.079572 -0.055613 0.021115

6 5.652432 -1.350673 -0.228178

6 7.001771 -1.533147 -0.235660

6 7.879167 -0.417745 0.008982

1 8.062319 1.673405 0.436141

1 5.003775 -2.205394 -0.415756

1 7.426140 -2.513770 -0.424945

1 8.952577 -0.591991 -0.003092

8 5.521190 2.251564 0.498850

6 3.728959 0.219727 0.045122

7 2.718694 -0.652653 -0.153106

1 3.461890 1.252162 0.246548

6 1.336831 -0.393417 -0.136010

6 0.462589 -1.463263 -0.381097

6 -0.912902 -1.272739 -0.378341

6 -1.458338 -0.001924 -0.126317

6 -0.574379 1.068486 0.088065

6 0.801342 0.883163 0.097382

1 0.866672 -2.450975 -0.590464

1 -1.564704 -2.109649 -0.607072

1 -0.988879 2.055783 0.263668

1 1.446455 1.734425 0.279109

7 -2.835114 0.272091 -0.121522

6 -3.702421 -0.614391 0.250379

6 -5.127696 -0.369902 0.202306

6 -6.026583 -1.368405 0.630526

6 -7.396565 -1.167575 0.594853

6 -7.894795 0.057805 0.123653

6 -7.038156 1.063476 -0.303214

6 -5.648534 0.868627 -0.271000

1 -5.620966 -2.310338 0.992403

1 -8.075996 -1.945489 0.926451

1 -8.967546 0.225845 0.091778

1 -7.413618 2.013566 -0.667785

1 -3.386872 -1.592788 0.635198

8 -4.849984 1.860149 -0.687416

1 -3.910530 1.543892 -0.585742

1 2.968738 -1.615116 -0.339112

E(S0)

-1031.71881902 Eh

E(S0)

-1031.72653511 Eh


7

DKR1

Optimized GAUSSIAN

DKR2

Optimized GAUSSIAN

6 -6.912668 1.334625 0.007502

6 -5.507005 1.009571 0.005524

6 -5.174924 -0.421958 -0.012719

6 -6.213913 -1.402901 -0.031214

6 -7.530957 -1.033597 -0.028892

6 -7.868735 0.354247 -0.008820

1 -7.172718 2.387919 0.022064

1 -5.934828 -2.454717 -0.046173

1 -8.317349 -1.780645 -0.041867

1 -8.919154 0.635305 -0.006895

8 -4.609484 1.904006 0.017052

6 -3.834499 -0.816498 -0.016870

7 -2.841054 0.072242 -0.003710

1 -3.582304 -1.874489 -0.039074

6 -1.461053 -0.163526 0.007969

6 -0.606564 0.941997 -0.131301

6 0.772868 0.789537 -0.133606

6 1.339272 -0.486077 0.012323

6 0.486920 -1.591649 0.154091

6 -0.892670 -1.438025 0.154322

1 -1.035163 1.932403 -0.250405

1 1.396808 1.666016 -0.260943

1 0.910424 -2.585214 0.277657

1 -1.515521 -2.316044 0.283434

7 2.726298 -0.710691 0.019818

6 3.713283 0.210912 0.032796

6 5.069869 -0.028458 0.001123

6 5.675132 -1.330629 -0.079595

6 7.028476 -1.475913 -0.107403

6 7.877912 -0.313833 -0.055978

6 7.369647 0.945156 0.018244

6 5.927872 1.191837 0.053494

1 5.047991 -2.220092 -0.126779

1 7.477509 -2.461700 -0.171435

1 8.955304 -0.459727 -0.079503

1 8.008866 1.821346 0.055743

1 3.417680 1.254193 0.081980

8 5.453443 2.334443 0.122714

1 -3.238109 1.051926 0.000647

1 3.002611 -1.683822 0.024729

6 -7.499612 -0.739260 -0.018782

6 -6.078116 -1.084247 -0.036909

6 -5.139399 0.075597 -0.003147

6 -5.654392 1.417376 0.045931

6 -6.994830 1.655235 0.059289

6 -7.921086 0.552919 0.025065

1 -8.197109 -1.570303 -0.043333

1 -4.968026 2.262499 0.078226

1 -7.375785 2.670516 0.098112

1 -8.986144 0.772327 0.036584

8 -5.682108 -2.258070 -0.078162

6 -3.802425 -0.257230 -0.021671

7 -2.752033 0.590962 -0.016529

1 -3.581676 -1.319603 -0.051757

6 -1.384718 0.264446 -0.004345

6 -0.450831 1.300667 -0.151088

6 0.914413 1.047761 -0.150230

6 1.384718 -0.264443 0.004400

6 0.450830 -1.300664 0.151144

6 -0.914413 -1.047758 0.150286

1 -0.797117 2.323004 -0.279572

1 1.600178 1.875924 -0.282195

1 0.797116 -2.323001 0.279627

1 -1.600179 -1.875921 0.282253

7 2.752032 -0.590960 0.016583

6 3.802426 0.257231 0.021715

6 5.139399 -0.075599 0.003200

6 5.654391 -1.417380 -0.045848

6 6.994828 -1.655240 -0.059251

6 7.921085 -0.552922 -0.025151

6 7.499612 0.739259 0.018663

6 6.078118 1.084242 0.036972

1 4.968023 -2.262503 -0.078099

1 7.375781 -2.670522 -0.098064

1 8.986142 -0.772327 -0.036756

1 8.197111 1.570305 0.043082

1 3.581679 1.319604 0.051792

8 5.682111 2.258076 0.077938

1 -2.955131 1.581833 -0.033175

1 2.955130 -1.581831 0.033239

E(S0)

-1031.71767403 Eh

E(S0)

-1031.70011001 Eh


8

Stable Structures (Excited State):

E

Optimized TURBOMOLE

E*

Optimized TURBOMOLE

6 7.037615 0.864544 -0.509497

6 5.638589 0.746567 -0.475750

6 5.046679 -0.347647 0.219335

6 5.885183 -1.283452 0.859977

6 7.265073 -1.159288 0.821120

6 7.834230 -0.076894 0.129755

1 7.468111 1.704556 -1.044921

1 5.424966 -2.115034 1.389519

1 7.897962 -1.887903 1.317516

1 8.915208 0.029242 0.092365

8 4.897793 1.672039 -1.099473

1 3.941307 1.423238 -0.960524

6 3.608800 -0.508500 0.275465

7 2.797685 0.328645 -0.288851

1 3.233262 -1.374135 0.836819

6 1.407235 0.127728 -0.276467

6 0.581498 1.264708 -0.306321

6 -0.802295 1.143172 -0.296888

6 -1.407235 -0.127728 -0.276467

6 -0.581498 -1.264708 -0.306321

6 0.802295 -1.143172 -0.296888

1 1.048727 2.244468 -0.335796

1 -1.418010 2.036247 -0.347382

1 -1.048727 -2.244468 -0.335796

1 1.418010 -2.036247 -0.347382

7 -2.797685 -0.328645 -0.288851

6 -3.608800 0.508500 0.275465

6 -5.046679 0.347647 0.219335

6 -5.885183 1.283452 0.859977

6 -7.265073 1.159288 0.821120

6 -7.834230 0.076894 0.129755

6 -7.037615 -0.864544 -0.509497

6 -5.638589 -0.746567 -0.475750

1 -5.424966 2.115034 1.389519

1 -7.897962 1.887903 1.317516

1 -8.915208 -0.029242 0.092365

1 -7.468111 -1.704556 -1.044921

1 -3.233262 1.374135 0.836819

8 -4.897793 -1.672039 -1.099473

1 -3.941307 -1.423238 -0.960524

6 6.947338 1.158574 -0.318179

6 5.564150 0.923417 -0.239281

6 5.061415 -0.430556 -0.253380

6 6.001248 -1.484034 -0.349769

6 7.362405 -1.234081 -0.429496

6 7.834865 0.094430 -0.414451

1 7.289469 2.188435 -0.304121

1 5.632162 -2.506880 -0.360062

1 8.064293 -2.059413 -0.501882

1 8.901858 0.289046 -0.477364

8 4.736349 1.962423 -0.149575

1 3.799379 1.578314 -0.091834

6 3.659045 -0.702439 -0.170047

7 2.777348 0.285507 -0.066390

1 3.352929 -1.751341 -0.171947

6 1.423811 0.097743 -0.060307

6 0.609148 1.232084 0.226770

6 -0.762069 1.148913 0.276436

6 -1.425779 -0.096349 0.029481

6 -0.612832 -1.222002 -0.294870

6 0.758724 -1.140670 -0.336570

1 1.111056 2.177575 0.412077

1 -1.340108 2.043426 0.482188

1 -1.115981 -2.161441 -0.505838

1 1.333594 -2.021002 -0.603157

7 -2.778004 -0.289418 0.061213

6 -3.642504 0.619357 0.498948

6 -5.052666 0.389911 0.422592

6 -5.972717 1.352071 0.902918

6 -7.341022 1.141158 0.835373

6 -7.841154 -0.054448 0.279820

6 -6.973667 -1.027299 -0.200331

6 -5.583895 -0.828667 -0.142817

1 -5.582226 2.272002 1.331779

1 -8.027399 1.894075 1.210906

1 -8.913856 -0.218154 0.227194

1 -7.337370 -1.954948 -0.630587

1 -3.312878 1.557307 0.952898

6 -4.775742 -1.777184 -0.612484

1 -3.828714 -1.445443 -0.465857

E(S0)

E(S1)

-1031.11748921 Eh

-1031.00104426 Eh

E(S1)

-1031.01120014 Eh


9

MK

Optimized TURBOMOLE

MK*

Optimized TURBOMOLE

6 -6.927566 1.223234 0.144415

6 -5.507373 0.963550 0.139566

6 -5.107850 -0.437907 -0.053499

6 -6.099146 -1.454418 -0.218615

6 -7.432864 -1.147199 -0.204264

6 -7.836504 0.211341 -0.020185

1 -7.237114 2.254104 0.284956

1 -5.770248 -2.482940 -0.357635

1 -8.182905 -1.921380 -0.330555

1 -8.899379 0.443240 -0.010742

8 -4.654022 1.887726 0.294089

6 -3.749827 -0.770739 -0.069225

7 -2.799150 0.150942 0.085786

1 -3.447778 -1.807301 -0.203757

6 -1.408399 -0.019982 0.081722

6 -0.616526 1.088972 0.423755

6 0.768815 0.992571 0.439661

6 1.407427 -0.217091 0.109581

6 0.607146 -1.329017 -0.205469

6 -0.777932 -1.234991 -0.235578

1 -1.100208 2.023358 0.694643

1 1.357040 1.852869 0.743973

1 1.096158 -2.267040 -0.449657

1 -1.358970 -2.108673 -0.511465

6 2.800377 -0.392995 0.111019

6 3.607882 0.579229 -0.174153

6 5.046530 0.429324 -0.122447

6 5.879664 1.518037 -0.455232

6 7.260403 1.406559 -0.415291

6 7.836373 0.182198 -0.036846

6 7.045570 -0.910476 0.295001

6 5.645584 -0.806815 0.257598

1 5.414418 2.457722 -0.745320

1 7.889124 2.252883 -0.672564

1 8.918222 0.084197 -0.002939

1 7.481405 -1.860239 0.587505

1 3.228338 1.560950 -0.486043

8 4.910473 -1.879222 0.579918

1 3.952822 -1.615873 0.487894

1 -3.240010 1.101290 0.220397

6 -6.969390 1.205612 0.093754

6 -5.552277 0.948064 0.083474

6 -5.145669 -0.447398 -0.010167

6 -6.100818 -1.443244 -0.081597

6 -7.496051 -1.149777 -0.067561

6 -7.911018 0.173520 0.019701

1 -7.273949 2.244965 0.162511

1 -5.785412 -2.482535 -0.150724

1 -8.214794 -1.959734 -0.125284

1 -8.970728 0.411264 0.030898

8 -4.703487 1.891524 0.152785

6 -3.732819 -0.805655 -0.030079

7 -2.798916 0.102476 0.036039

1 -3.447743 -1.851650 -0.101981

6 -1.395844 -0.032887 0.026728

6 -0.630186 1.139339 0.137202

6 0.752749 1.085402 0.132582

6 1.435949 -0.160076 0.008901

6 0.633357 -1.331956 -0.087010

6 -0.745108 -1.280740 -0.082589

1 -1.134034 2.098689 0.235067

1 1.311086 2.007608 0.245129

1 1.144417 -2.285753 -0.174084

1 -1.309441 -2.204841 -0.166779

6 2.796022 -0.331178 -0.012538

6 3.652258 0.681655 -0.092588

6 5.066268 0.476131 -0.058125

6 5.958118 1.574896 -0.156049

6 7.332017 1.401509 -0.123260

6 7.864047 0.107722 0.009430

6 7.020203 -0.997349 0.106655

6 5.629911 -0.837241 0.074904

1 5.535684 2.572495 -0.257839

1 7.993144 2.259868 -0.199146

1 8.940762 -0.036867 0.036000

1 7.414499 -2.003817 0.208434

1 3.310644 1.714192 -0.212157

8 4.846323 -1.924016 0.167743

1 3.899487 -1.593203 0.119078

1 -3.219263 1.062984 0.102543

E(S0)

E(S1)

-1031.10941466 Eh

-1031.00802837 Eh

E(S1)

-1031.01727473 Eh


10

DK*

Optimized TURBOMOLE

ER

Optimized TURBOMOLE

6 6.989175 1.160213 0.019326

6 5.564855 0.930288 0.012772

6 5.127706 -0.461465 -0.005741

6 6.061875 -1.482222 -0.016941

6 7.456208 -1.213920 -0.010757

6 7.901827 0.107634 0.007486

1 7.314639 2.195190 0.033454

1 5.725183 -2.516649 -0.030634

1 8.160870 -2.038063 -0.020126

1 8.967115 0.318673 0.012600

8 4.736998 1.890765 0.022517

6 3.710257 -0.787653 -0.011611

7 2.793733 0.134443 0.001475

1 3.405908 -1.830884 -0.027039

6 1.382198 0.019244 0.001645

6 0.636535 1.205354 -0.005426

6 -0.748507 1.175561 -0.007169

6 -1.440140 -0.066783 -0.001151

6 -0.663038 -1.260520 0.007463

6 0.714730 -1.222522 0.008886

1 1.151931 2.163276 -0.010447

1 -1.296698 2.109603 -0.012491

1 -1.179733 -2.215514 0.014136

1 1.264123 -2.159288 0.018156

6 -2.795227 -0.180091 -0.001956

6 -3.736834 0.819268 -0.008746

6 -5.096535 0.503497 -0.004762

6 -6.083343 1.537965 -0.011738

6 -7.428491 1.249058 -0.007106

6 -7.856819 -0.105250 0.004765

6 -6.945922 -1.142049 0.011572

6 -5.531971 -0.909033 0.007118

1 -5.744447 2.572874 -0.020708

1 -8.162094 2.050243 -0.012397

1 -8.922018 -0.325623 0.008514

1 -7.266818 -2.179627 0.020601

1 -3.404021 1.851938 -0.017433

8 -4.689562 -1.870760 0.013160

1 3.223207 1.090459 0.013364

1 -3.296855 -1.117630 0.005367

6 6.206425 0.631281 1.093855

6 4.864672 0.236959 0.965073

6 4.286167 0.143135 -0.333826

6 5.078140 0.454796 -1.458293

6 6.401324 0.844120 -1.321638

6 6.958970 0.928887 -0.035116

1 6.628136 0.695351 2.091748

1 4.627628 0.382910 -2.445982

1 6.998940 1.081112 -2.195988

1 7.995855 1.232512 0.082930

8 4.164049 -0.038656 2.072910

1 3.242233 -0.286448 1.782309

6 2.906734 -0.260392 -0.510653

7 2.135097 -0.540001 0.490825

1 2.535246 -0.303276 -1.543037

6 0.815354 -0.981879 0.297734

6 -0.141991 -0.636884 1.268120

6 -1.468255 -1.025280 1.135567

6 -1.877763 -1.809834 0.036624

6 -0.904610 -2.212722 -0.899738

6 0.415505 -1.788034 -0.783407

1 0.173132 -0.039641 2.118415

1 -2.197935 -0.742179 1.887292

1 -1.204002 -2.870634 -1.709924

1 1.150892 -2.126910 -1.507037

7 -3.177539 -2.324726 -0.078069

6 -4.252390 -1.628283 -0.016617

6 -4.520515 -0.171294 0.021881

6 -5.685435 0.214134 0.721085

6 -6.090263 1.537502 0.816514

6 -5.338589 2.524105 0.165981

6 -4.206982 2.176654 -0.559618

6 -3.786340 0.840378 -0.646580

1 -6.270214 -0.564286 1.206031

1 -6.982212 1.799716 1.376694

1 -5.642550 3.565995 0.217400

1 -3.620767 2.922737 -1.086371

1 -5.171498 -2.223244 0.022607

8 -2.709673 0.622708 -1.440562

1 -2.334978 -0.260387 -1.299139

E(S1)

-1031.01158215 Eh

E(S0)

E(S1)

-1031.09195084 Eh

-1030.92083027 Eh


11

MKR1

Optimized TURBOMOLE

6 5.971685 -1.503617 -0.743236

6 4.638816 -0.951370 -0.692927

6 4.424216 0.129435 0.280130

6 5.498320 0.576636 1.110671

6 6.742752 0.014332 1.016953

6 6.966826 -1.036530 0.074781

1 6.144940 -2.302754 -1.457095

1 5.305841 1.378367 1.821519

1 7.556595 0.357096 1.647755

1 7.960026 -1.475663 0.009431

8 3.706886 -1.373093 -1.441379

6 3.159095 0.715139 0.390181

7 2.134957 0.321453 -0.367088

1 2.991798 1.510119 1.113876

6 0.822112 0.811105 -0.383112

6 -0.111791 0.143482 -1.194081

6 -1.433094 0.564096 -1.251769

6 -1.865339 1.678873 -0.504262

6 -0.913630 2.367981 0.273809

6 0.404578 1.932053 0.352040

1 0.209440 -0.716041 -1.776051

1 -2.140695 0.039589 -1.885502

1 -1.229526 3.255214 0.813942

1 1.104875 2.488776 0.965867

6 -3.157272 2.212914 -0.613600

6 -4.245648 1.541580 -0.510421

6 -4.547175 0.148668 -0.106181

6 -5.683187 -0.431535 -0.712743

6 -6.110870 -1.715743 -0.409200

6 -5.416055 -2.449979 0.560394

6 -4.316613 -1.896604 1.203190

6 -3.872115 -0.603551 0.887652

1 -6.224765 0.156888 -1.449820

1 -6.977530 -2.137905 -0.907827

1 -5.739883 -3.453367 0.822568

1 -3.775912 -2.440443 1.970891

1 -5.146559 2.104271 -0.779270

8 -2.832397 -0.150091 1.630119

1 -2.446607 0.651521 1.246586

1 2.442904 -0.461303 -1.006789

E(S0)

E(S1)

-1031.08357418 Eh

-1030.97936330 Eh


12

MKR2

Optimized TURBOMOLE

MKR2*

Optimized TURBOMOLE

6 7.443967 1.009556 0.250304

6 6.008776 1.297219 0.252821

6 5.122064 0.121981 0.006456

6 5.695192 -1.178844 -0.213761

6 7.044733 -1.364171 -0.201351

6 7.921972 -0.246005 0.035511

1 8.104090 1.852851 0.428709

1 5.046531 -2.035783 -0.393615

1 7.469480 -2.349161 -0.368362

1 8.995523 -0.422829 0.040726

8 5.562614 2.437499 0.446576

6 3.771143 0.399498 0.014233

7 2.761070 -0.475392 -0.178900

1 3.503786 1.435895 0.196840

6 1.378673 -0.216505 -0.165279

6 0.505000 -1.286906 -0.413964

6 -0.871290 -1.097849 -0.410475

6 -1.418393 0.172186 -0.154454

6 -0.534824 1.243545 0.061529

6 0.841745 1.059675 0.070279

1 0.910228 -2.274001 -0.626093

1 -1.522147 -1.935512 -0.641386

1 -0.950524 2.230150 0.240800

1 1.486070 1.911403 0.255359

7 -2.795731 0.444560 -0.141950

6 -3.661516 -0.446257 0.225376

6 -5.087257 -0.199343 0.191227

6 -5.985189 -1.202402 0.612711

6 -7.355467 -0.996856 0.592745

6 -7.854576 0.237713 0.144732

6 -6.998591 1.247652 -0.275481

6 -5.608601 1.048248 -0.259294

1 -5.578923 -2.151317 0.956520

1 -8.034686 -1.777985 0.918737

1 -8.927570 0.409441 0.126109

1 -7.374830 2.204701 -0.621907

1 -3.343769 -1.429547 0.596698

8 -4.809850 2.042812 -0.667740

1 -3.870612 1.720371 -0.577938

1 3.011688 -1.440294 -0.353046

6 -7.327862 -0.688889 1.253024

6 -5.878049 -0.781504 1.306695

6 -5.129940 -0.149656 0.207604

6 -5.810391 0.491826 -0.817486

6 -7.215725 0.551439 -0.821829

6 -7.962492 -0.039786 0.215300

1 -7.875163 -1.154043 2.065101

1 -5.276874 0.959089 -1.640358

1 -7.723792 1.057893 -1.634435

1 -9.045817 0.019350 0.190835

8 -5.292465 -1.367702 2.238866

6 -3.687144 -0.265536 0.300710

7 -2.818600 0.223488 -0.512810

1 -3.298103 -0.823476 1.149473

6 -1.367313 0.074417 -0.390729

6 -0.623544 1.063117 0.257704

6 0.757713 0.966127 0.310259

6 1.459905 -0.124675 -0.307872

6 0.647603 -1.093848 -0.980019

6 -0.727422 -1.001287 -1.032859

1 -1.124225 1.908553 0.725143

1 1.310369 1.745520 0.820690

1 1.154509 -1.928106 -1.454799

1 -1.307325 -1.756751 -1.557351

7 2.799827 -0.305293 -0.321168

6 3.657929 0.501109 0.347853

6 5.064998 0.328938 0.255883

6 5.958068 1.171638 0.973366

6 7.334684 1.023898 0.891560

6 7.881961 0.017680 0.081519

6 7.037124 -0.833326 -0.638752

6 5.649933 -0.698633 -0.566809

1 5.531019 1.952331 1.600397

1 7.985924 1.687547 1.454543

1 8.959144 -0.104933 0.010925

1 7.436451 -1.621061 -1.271075

1 3.300756 1.298205 1.004090

8 4.870073 -1.542180 -1.274636

1 3.920097 -1.272586 -1.071744

1 -3.163553 0.753735 -1.312910

E(S0)

E(S1)

-1031.09134748 Eh

-1030.99046611 Eh

E(S1)

-1031.00610148 Eh


13

DKR1

Optimized TURBOMOLE

DKR2

Optimized TURBOMOLE

6 -6.872557 1.520565 -0.004393

6 -5.467309 1.190777 -0.002290

6 -5.139546 -0.242263 0.005039

6 -6.181693 -1.220792 0.007120

6 -7.498340 -0.847099 0.004854

6 -7.832215 0.542595 -0.000697

1 -7.129161 2.575180 -0.009227

1 -5.905868 -2.274092 0.011443

1 -8.287458 -1.592131 0.007235

1 -8.882255 0.826693 -0.002287

8 -4.566307 2.082610 -0.008026

6 -3.799244 -0.640047 0.005233

7 -2.804526 0.248168 0.000511

1 -3.549358 -1.699186 0.003029

6 -1.424346 0.011450 0.007609

6 -0.569423 1.118770 -0.121132

6 0.810636 0.966364 -0.127367

6 1.377400 -0.311213 0.003857

6 0.524687 -1.418880 0.133479

6 -0.855540 -1.265341 0.137284

1 -0.998437 2.110816 -0.227801

1 1.434347 1.844795 -0.245640

1 0.948775 -2.414268 0.243402

1 -1.478011 -2.145913 0.253626

7 2.765006 -0.535820 0.008746

6 3.751291 0.387268 0.034279

6 5.109118 0.151051 0.007227

6 5.718624 -1.149231 -0.079263

6 7.073205 -1.290458 -0.099621

6 7.919517 -0.125899 -0.035054

6 7.406787 1.131546 0.044825

6 5.963433 1.373923 0.073563

1 5.094195 -2.040525 -0.135804

1 7.525770 -2.274945 -0.167368

1 8.997931 -0.268882 -0.052964

1 8.043193 2.009804 0.092167

1 3.453921 1.430074 0.091359

8 5.485249 2.514869 0.148822

1 -3.202825 1.228900 -0.010091

1 3.041334 -1.509228 0.004320

6 -7.502842 -0.740202 -0.020468

6 -6.080518 -1.084712 -0.035912

6 -5.142352 0.076214 -0.001382

6 -5.658107 1.418376 0.046061

6 -6.999355 1.655703 0.057234

6 -7.925537 0.552326 0.022163

1 -8.199953 -1.572097 -0.046209

1 -4.971850 2.264190 0.078737

1 -7.381124 2.671193 0.094673

1 -8.991199 0.771277 0.031884

8 -5.683746 -2.258666 -0.075752

6 -3.804680 -0.256860 -0.017889

7 -2.753522 0.591648 -0.011965

1 -3.584904 -1.320005 -0.046585

6 -1.385646 0.264871 -0.001288

6 -0.451446 1.302414 -0.143138

6 0.914607 1.050070 -0.143515

6 1.385643 -0.263423 0.003888

6 0.451444 -1.300928 0.145985

6 -0.914601 -1.048567 0.146550

1 -0.797930 2.325750 -0.266350

1 1.600145 1.879876 -0.270125

1 0.797922 -2.324291 0.269008

1 -1.600149 -1.878280 0.273758

7 2.753447 -0.590460 0.013764

6 3.804966 0.257603 0.016406

6 5.142446 -0.076241 -0.000138

6 5.657399 -1.418861 -0.043199

6 6.998501 -1.657028 -0.054121

6 7.925350 -0.554088 -0.022991

6 7.503430 0.738831 0.015312

6 6.081310 1.084250 0.029792

1 4.970635 -2.264390 -0.072441

1 7.379651 -2.672861 -0.088493

1 8.990880 -0.773707 -0.032237

1 8.201044 1.570392 0.038012

1 3.585762 1.320935 0.041976

8 5.685260 2.258586 0.065215

1 -2.956605 1.582888 -0.027730

1 2.956224 -1.581727 0.031511

E(S0)

E(S1)

-1031.08243072 Eh

-1031.13341903 Eh

E(S0)

E(S1)

-1031.06480619 Eh

-1031.11714720 Eh


14

Possible Degeneracy Points (“Conical Intersections”):

CI E↔ER

TURBOMOLE

CI MK↔MKR1

TURBOMOLE

6 -6.347102 1.134666 1.005702

6 -5.025080 0.927391 0.579264

6 -4.639996 -0.359026 0.082013

6 -5.604005 -1.396102 0.055150

6 -6.897802 -1.182148 0.490389

6 -7.264061 0.094565 0.960188

1 -6.619195 2.118253 1.373575

1 -5.306440 -2.371005 -0.323556

1 -7.624394 -1.987616 0.471928

1 -8.282126 0.270762 1.296288

8 -4.153991 1.934693 0.674882

1 -3.270082 1.588556 0.367210

6 -3.318732 -0.597517 -0.421856

7 -2.341421 0.258932 -0.222730

1 -3.123246 -1.598768 -0.819812

6 -1.049313 0.050797 -0.638662

6 -0.109137 1.075949 -0.312967

6 1.208534 0.981895 -0.661320

6 1.703422 -0.172078 -1.391535

6 0.728451 -1.202099 -1.719982

6 -0.581257 -1.096127 -1.357475

1 -0.476394 1.944410 0.225188

1 1.894840 1.773991 -0.391336

1 1.082971 -2.064138 -2.274605

1 -1.264705 -1.893515 -1.629374

7 2.926486 -0.350014 -1.805479

6 3.946746 0.515696 -1.350956

6 4.740683 0.312436 -0.214331

6 5.690071 1.310302 0.185267

6 6.458551 1.171305 1.324717

6 6.324475 0.026097 2.130474

6 5.427140 -0.981486 1.764812

6 4.653197 -0.865294 0.614743

1 5.790066 2.196981 -0.435177

1 7.165734 1.948596 1.598952

1 6.918017 -0.081400 3.033018

1 5.321991 -1.884803 2.357367

1 4.202646 1.369284 -1.976571

8 3.876454 -1.926460 0.261793

1 3.446590 -1.720460 -0.588968

6 -6.512668 0.586872 -0.404304

6 -5.086919 0.350227 -0.464042

6 -4.659072 -1.051801 -0.642830

6 -5.639776 -2.085938 -0.743583

6 -6.976908 -1.798058 -0.679904

6 -7.406392 -0.443231 -0.508406

1 -6.833312 1.615131 -0.273118

1 -5.301227 -3.111557 -0.873834

1 -7.716508 -2.588557 -0.757837

1 -8.472618 -0.235028 -0.459183

8 -4.248724 1.289604 -0.367677

6 -3.297804 -1.368654 -0.698857

7 -2.347179 -0.428458 -0.596413

1 -2.985214 -2.402331 -0.817201

6 -0.975095 -0.568621 -0.626375

6 -0.184904 0.577790 -0.332881

6 1.183051 0.507753 -0.298867

6 1.883087 -0.727868 -0.597045

6 1.046313 -1.875184 -0.901010

6 -0.319758 -1.796552 -0.920934

1 -0.688846 1.516182 -0.115715

1 1.768234 1.392339 -0.078482

1 1.550991 -2.802112 -1.150319

1 -0.896809 -2.676243 -1.188441

7 3.188035 -0.880895 -0.656930

6 4.118285 0.154600 -0.699993

6 4.792702 0.813710 0.332690

6 5.754341 1.826138 -0.001391

6 6.370165 2.586942 0.971089

6 6.064066 2.378419 2.327924

6 5.155437 1.381004 2.697268

6 4.543325 0.589506 1.733953

1 5.982055 1.987858 -1.052132

1 7.091429 3.348452 0.688534

1 6.540070 2.981200 3.094491

1 4.907211 1.202556 3.738409

1 4.347517 0.494055 -1.714365

8 3.679744 -0.380426 2.142307

1 3.378280 -0.875724 1.363545

1 -2.794604 0.516899 -0.468140

E(S0)

E(S1)

-1031.03501872 Eh

-1031.03017321 Eh

E(S0)

E(S1)

-1031.03413797 Eh

-1031.02955865 Eh


15

CI MK↔MKR2

TURBOMOLE

CI DK↔DKR1

TURBOMOLE

6 -6.507228 2.782405 1.795878

6 -5.091733 2.474476 1.807022

6 -4.790715 1.055033 1.661638

6 -5.778722 0.079006 1.531207

6 -7.128944 0.443473 1.527763

6 -7.472974 1.803888 1.663486

1 -6.770252 3.832267 1.888362

1 -5.492877 -0.967159 1.434856

1 -7.901758 -0.309214 1.411501

1 -8.524177 2.083289 1.661632

8 -4.176828 3.328615 1.934044

6 -3.365443 0.708588 1.699289

7 -2.649674 0.675264 0.619262

1 -2.852664 0.463502 2.630216

6 -1.268939 0.353330 0.425703

6 -0.740643 0.557337 -0.859680

6 0.583201 0.254344 -1.124724

6 1.417316 -0.273004 -0.100392

6 0.865885 -0.444259 1.197005

6 -0.456377 -0.151981 1.463929

1 -1.371581 0.971816 -1.642922

1 0.991966 0.451067 -2.109781

1 1.507944 -0.832672 1.980637

1 -0.848570 -0.314219 2.462028

7 2.757101 -0.589495 -0.281779

6 3.211407 -1.011344 -1.434766

6 4.606662 -1.239823 -1.671519

6 5.022634 -1.707776 -2.933650

6 6.387806 -1.951440 -3.199673

6 7.341673 -1.718241 -2.176651

6 6.968513 -1.260091 -0.927394

6 5.587443 -1.011548 -0.649609

1 4.271750 -1.872234 -3.701891

1 6.703822 -2.309524 -4.172820

1 8.394635 -1.900545 -2.376757

1 7.695163 -1.082332 -0.142201

1 2.526730 -1.246286 -2.259520

8 5.256921 -0.583675 0.584386

1 4.269090 -0.480254 0.598001

1 -3.177561 0.939413 -0.212116

6 6.777589 -2.157509 1.616635

6 5.528528 -1.422362 1.625385

6 4.340288 -2.291092 1.669740

6 4.433056 -3.691099 1.687767

6 5.671574 -4.327710 1.670076

6 6.838541 -3.536078 1.637355

1 7.679772 -1.552726 1.594487

1 3.517639 -4.280586 1.717479

1 5.739217 -5.410820 1.682333

1 7.809061 -4.029044 1.627085

8 5.447617 -0.172011 1.572765

6 3.048008 -1.626029 1.727045

7 2.419418 -1.284021 0.624031

1 2.572206 -1.359278 2.670677

6 1.181060 -0.632628 0.435000

6 0.756565 -0.401476 -0.881545

6 -0.450393 0.229442 -1.142797

6 -1.267583 0.648259 -0.076516

6 -0.834432 0.415020 1.242653

6 0.371845 -0.215643 1.502746

1 1.382558 -0.719053 -1.711507

1 -0.745293 0.391646 -2.172400

1 -1.453861 0.735646 2.076468

1 0.672106 -0.372769 2.532413

7 -2.495727 1.287213 -0.264414

6 -3.096369 1.604688 -1.438355

6 -4.308641 2.234993 -1.598710

6 -5.162644 2.674050 -0.525664

6 -6.348916 3.291035 -0.782216

6 -6.768455 3.514626 -2.143678

6 -6.009543 3.124950 -3.202681

6 -4.721452 2.455119 -3.019136

1 -4.863224 2.515011 0.509879

1 -6.987659 3.619482 0.031741

1 -7.721228 4.010342 -2.316030

1 -6.323684 3.292639 -4.228159

1 -2.576003 1.338886 -2.353121

8 -4.020389 2.094052 -3.974415

1 2.951652 -1.533350 -0.208855

1 -2.982805 1.538184 0.586440

E(S0)

E(S1)

-1031.03150361 Eh

-1031.03098295 Eh

E(S0)

E(S1)

-1031.00654820 Eh

-1031.00469789 Eh


16

CI DKR1↔DKR2

TURBOMOLE

6 -7.438535 -0.999500 0.019078

6 -6.008867 -1.304540 -0.041893

6 -5.103738 -0.114825 -0.010096

6 -5.652123 1.212198 0.072261

6 -6.998015 1.409463 0.121783

6 -7.894413 0.281227 0.094461

1 -8.115121 -1.848132 0.000590

1 -4.986622 2.074929 0.100960

1 -7.405505 2.413643 0.185130

1 -8.965200 0.468406 0.136408

8 -5.579287 -2.470128 -0.116694

6 -3.761352 -0.393022 -0.064322

7 -2.766235 0.525744 -0.079720

1 -3.482141 -1.441473 -0.104553

6 -1.389159 0.293195 -0.092503

6 -0.528937 1.397017 -0.244675

6 0.847796 1.238069 -0.264683

6 1.400640 -0.045388 -0.143541

6 0.550976 -1.148539 0.014460

6 -0.826977 -0.990088 0.040260

1 -0.951025 2.391708 -0.359960

1 1.478299 2.113357 -0.374570

1 0.972736 -2.143014 0.136884

1 -1.451714 -1.864341 0.174628

7 2.793344 -0.282202 -0.160651

6 3.802233 0.570087 -0.195368

6 5.175898 0.135276 -0.076062

6 5.987560 -0.095201 -1.199759

6 7.323592 -0.434141 -1.048292

6 7.851420 -0.576947 0.261011

6 7.070253 -0.403992 1.378735

6 5.673896 -0.013262 1.303482

1 5.560115 -0.015168 -2.198933

1 7.962923 -0.555927 -1.916530

1 8.907325 -0.812492 0.377616

1 7.459937 -0.569211 2.379884

1 3.544463 1.626517 -0.191819

8 4.940636 0.131312 2.305778

1 -3.067728 1.500914 -0.103683

1 3.068652 -1.261527 -0.115101

E(S0)

E(S1)

-1031.00573372 Eh

-1031.00325583 Eh


17

Maxima on the Proton-Transfer Coordinates:

Transition State Structure E→MK

Optimized GAUSSIAN

Transition State Structure E*→MK*

Optimized TURBOMOLE

6 -6.852665 -1.166304 -0.385161

6 -5.460374 -0.865815 -0.308024

6 -5.090766 0.427824 0.237742

6 -6.092201 1.333773 0.673725

6 -7.424564 1.006004 0.581616

6 -7.792070 -0.255610 0.045957

1 -7.137073 -2.130517 -0.793004

1 -5.785687 2.295226 1.080673

1 -8.190246 1.699372 0.912692

1 -8.846810 -0.509338 -0.024726

8 -4.556097 -1.701179 -0.700995

1 -3.437905 -1.067709 -0.459366

6 -3.714359 0.743783 0.327467

7 -2.818008 -0.130491 -0.083520

1 -3.400483 1.700180 0.748196

6 -1.426604 0.034027 -0.089735

6 -0.637271 -1.116124 -0.252287

6 0.748423 -1.029810 -0.268192

6 1.389232 0.213484 -0.119723

6 0.593937 1.366156 -0.000615

6 -0.791006 1.282961 0.021009

1 -1.126671 -2.078104 -0.369874

1 1.336025 -1.927997 -0.428581

1 1.086837 2.329853 0.077455

1 -1.375068 2.194248 0.095096

7 2.782765 0.381161 -0.137251

6 3.582278 -0.536167 0.305684

6 5.021489 -0.404051 0.239633

6 5.845021 -1.430917 0.745232

6 7.225989 -1.336677 0.695153

6 7.812179 -0.192415 0.130481

6 7.031256 0.838747 -0.373975

6 5.631115 0.751637 -0.328147

1 5.371712 -2.309030 1.178239

1 7.846944 -2.135412 1.086515

1 8.894356 -0.108564 0.086350

1 7.475153 1.726772 -0.810920

1 3.195387 -1.453375 0.767630

8 4.906085 1.764558 -0.820503

1 3.946100 1.525636 -0.696036

6 6.842840 1.255550 -0.055444

6 5.469466 0.890201 -0.080769

6 5.096028 -0.488879 -0.330120

6 6.108622 -1.411784 -0.538354

6 7.471699 -1.031595 -0.509993

6 7.830887 0.299384 -0.268234

1 7.081098 2.296861 0.134796

1 5.850183 -2.450936 -0.727045

1 8.237442 -1.782539 -0.677162

1 8.877610 0.585834 -0.246880

8 4.544136 1.790613 0.119476

1 3.566197 1.209867 0.042226

6 3.684016 -0.855633 -0.350417

7 2.793223 0.087848 -0.142282

1 3.411779 -1.894537 -0.533091

6 1.422771 -0.049758 -0.115584

6 0.652676 1.113266 0.135387

6 -0.724163 1.069420 0.189919

6 -1.423229 -0.160894 -0.003667

6 -0.640424 -1.320594 -0.271846

6 0.734164 -1.278714 -0.324745

1 1.173626 2.056125 0.282727

1 -1.271790 1.988350 0.367983

1 -1.168020 -2.256893 -0.428443

1 1.284415 -2.192243 -0.527602

7 -2.783847 -0.323435 0.036797

6 -3.624667 0.636970 0.392738

6 -5.041759 0.433615 0.380502

6 -5.922613 1.472252 0.772129

6 -7.296863 1.297848 0.768981

6 -7.838862 0.062880 0.369676

6 -7.007130 -0.982649 -0.020719

6 -5.614798 -0.820543 -0.023434

1 -5.493266 2.423635 1.079211

1 -7.951814 2.109118 1.072774

1 -8.916131 -0.079943 0.365552

1 -7.408580 -1.942422 -0.330761

1 -3.272611 1.617321 0.727134

8 -4.841854 -1.846368 -0.403261

1 -3.890455 -1.526598 -0.328154

E(S0)

-1031.74300623 Eh

E(S1)

-1031.00945537 Eh


18

Transition State Structure MK→DK

Optimized GAUSSIAN

Transition State Structure MK*→DK*

Optimized TURBOMOLE

6 -6.940209 1.141998 0.057194

6 -5.513887 0.923536 0.056068

6 -5.074479 -0.475694 -0.044050

6 -6.036875 -1.528831 -0.130761

6 -7.377826 -1.259465 -0.124382

6 -7.819492 0.095781 -0.029086

1 -7.278813 2.170289 0.129745

1 -5.679296 -2.554171 -0.202636

1 -8.105585 -2.061127 -0.190571

1 -8.888110 0.296840 -0.025261

8 -4.687354 1.880322 0.136966

6 -3.708812 -0.770004 -0.052370

7 -2.783958 0.187192 0.028650

1 -3.379162 -1.804033 -0.123828

6 -1.390477 0.058915 0.024626

6 -0.630359 1.229977 0.182957

6 0.755990 1.183272 0.190845

6 1.426666 -0.040693 0.029324

6 0.664196 -1.211422 -0.117125

6 -0.722781 -1.167388 -0.122985

1 -1.140480 2.179593 0.314127

1 1.311375 2.102105 0.344977

1 1.176264 -2.160604 -0.239825

1 -1.274924 -2.091858 -0.249519

7 2.820530 -0.169214 0.021766

6 3.704492 0.797314 -0.132748

6 5.084989 0.494527 -0.087153

6 6.072840 1.499992 -0.255247

6 7.410262 1.184269 -0.214848

6 7.797867 -0.164980 -0.005125

6 6.873013 -1.172299 0.159333

6 5.475328 -0.888187 0.125634

1 5.751193 2.527020 -0.415199

1 8.165363 1.952650 -0.341328

1 8.856914 -0.408420 0.025725

1 7.172881 -2.202659 0.318432

1 3.376825 1.822610 -0.309730

8 4.584325 -1.811838 0.273514

1 3.452626 -1.156817 0.168532

1 -3.251520 1.131171 0.099008

6 6.985066 1.142315 0.016528

6 5.560429 0.919981 0.012326

6 5.117737 -0.468696 -0.005552

6 6.046634 -1.493138 -0.018015

6 7.444783 -1.233072 -0.014107

6 7.895262 0.084674 0.003199

1 7.315982 2.175661 0.030004

1 5.704574 -2.525945 -0.031046

1 8.144395 -2.061486 -0.024565

1 8.961250 0.292513 0.006530

8 4.736587 1.885327 0.023435

6 3.697492 -0.789090 -0.009911

7 2.786421 0.139305 0.004542

1 3.387345 -1.830580 -0.025766

6 1.375196 0.033437 0.005328

6 0.637375 1.225420 -0.000640

6 -0.747510 1.203392 -0.002452

6 -1.451423 -0.033884 0.002255

6 -0.679416 -1.231038 0.010189

6 0.699138 -1.204149 0.011651

1 1.160309 2.179411 -0.004734

1 -1.288320 2.142249 -0.006694

1 -1.204723 -2.181146 0.015948

1 1.242882 -2.144311 0.020115

7 -2.809000 -0.151445 0.000871

6 -3.714867 0.857309 -0.008438

6 -5.085083 0.536083 -0.005672

6 -6.094120 1.539890 -0.015593

6 -7.433490 1.207853 -0.012374

6 -7.816131 -0.154127 0.000980

6 -6.868142 -1.165353 0.010775

6 -5.480186 -0.870826 0.007792

1 -5.786082 2.584100 -0.025773

1 -8.191820 1.985535 -0.019988

1 -8.872663 -0.411465 0.003601

1 -7.155368 -2.212473 0.020968

1 -3.392397 1.896477 -0.018592

8 -4.579401 -1.810177 0.016608

1 3.223973 1.092628 0.016307

1 -3.472688 -1.151163 0.009959

E(S0)

-1031.73470056 Eh

E(S1)

-1031.01012824 Eh


19

Maxima on the Way to the Conical Intersections:

Maximum on Path to CI: E*↔ER*

Optimized TURBOMOLE

Maximum on Path to CI: MK*↔MKR1*

Optimized TURBOMOLE

6 6.847183 1.025810 -1.159018

6 5.510572 0.867546 -0.770196

6 5.022556 -0.433868 -0.380495

6 5.937467 -1.521824 -0.414545

6 7.250728 -1.348366 -0.812364

6 7.706840 -0.068728 -1.187978

1 7.181534 2.019314 -1.440834

1 5.579423 -2.505339 -0.118782

1 7.930840 -2.194837 -0.830969

1 8.738521 0.067983 -1.499945

8 4.709062 1.938813 -0.758756

1 3.814108 1.630124 -0.420132

6 3.677118 -0.623983 0.034276

7 2.806548 0.391938 0.107193

1 3.375041 -1.632960 0.330814

6 1.459783 0.216062 0.109910

6 0.637835 1.317352 0.506434

6 -0.730889 1.218126 0.550734

6 -1.386876 -0.003079 0.193785

6 -0.573119 -1.089193 -0.235054

6 0.798227 -0.993054 -0.284077

1 1.136492 2.242882 0.779106

1 -1.312490 2.083887 0.849638

1 -1.071783 -2.010192 -0.524447

1 1.389337 -1.829779 -0.641510

7 -2.741096 -0.212664 0.220801

6 -3.619587 0.658201 0.684959

6 -5.026040 0.384106 0.633061

6 -5.963270 1.317158 1.133669

6 -7.324835 1.064706 1.092512

6 -7.797662 -0.145438 0.542226

6 -6.912926 -1.089132 0.041027

6 -5.527791 -0.848055 0.074004

1 -5.592148 2.247420 1.557110

1 -8.027299 1.794471 1.483029

1 -8.865696 -0.341757 0.510768

1 -7.256633 -2.025762 -0.385773

1 -3.315117 1.607617 1.133486

8 -4.701156 -1.768995 -0.413097

1 -3.762799 -1.406508 -0.290571

6 -6.547266 1.118134 2.868515

6 -5.190772 0.864440 2.442578

6 -4.909966 -0.465915 1.909679

6 -5.918892 -1.412034 1.833208

6 -7.235878 -1.121738 2.262060

6 -7.533327 0.144410 2.775957

1 -6.756086 2.106518 3.264319

1 -5.698450 -2.400173 1.435064

1 -8.004582 -1.883030 2.188330

1 -8.543797 0.367517 3.105479

8 -4.292073 1.751879 2.527611

6 -3.572199 -0.809692 1.458772

7 -2.585884 0.029385 1.512301

1 -3.388639 -1.805956 1.064148

6 -1.225857 -0.127507 1.120463

6 -0.373771 0.965636 1.311797

6 0.964056 0.888274 0.953278

6 1.500322 -0.293450 0.363443

6 0.601589 -1.390593 0.185959

6 -0.724918 -1.315030 0.556337

1 -0.763255 1.881463 1.752351

1 1.622707 1.727984 1.144960

1 0.998527 -2.299650 -0.254348

1 -1.365091 -2.178860 0.398713

7 2.797066 -0.451539 -0.008286

6 3.645025 0.598594 -0.108216

6 4.992187 0.543060 0.313803

6 5.857032 1.669652 0.179253

6 7.171528 1.630153 0.606703

6 7.687411 0.451845 1.177224

6 6.879188 -0.679688 1.309698

6 5.548270 -0.658524 0.887062

1 5.451418 2.576574 -0.264198

1 7.805166 2.506230 0.500212

1 8.719856 0.416366 1.513215

1 7.261999 -1.600393 1.739388

1 3.281350 1.551516 -0.511499

8 4.801137 -1.769061 1.016153

1 3.895115 -1.545127 0.641120

1 -2.887785 0.947692 1.909145

E(S1)

-1031.01038856 Eh

E(S1)

-1031.01147311 Eh


20

Maximum on Path to CI: MK↔MKR2

Optimized TURBOMOLE

Maximum on Path to CI: DK↔DKR1

Optimized TURBOMOLE

6 -6.856957 1.200733 -0.313568

6 -5.486904 0.860423 -0.482509

6 -5.123368 -0.526092 -0.207709

6 -6.044059 -1.376439 0.350288

6 -7.422516 -1.006687 0.494486

6 -7.810671 0.267125 0.142472

1 -7.158325 2.196393 -0.624830

1 -5.734010 -2.369455 0.667257

1 -8.141400 -1.743414 0.837598

1 -8.851409 0.568023 0.227147

8 -4.576144 1.707401 -0.803384

6 -3.689737 -0.878142 -0.346204

7 -2.819321 0.016521 0.096529

1 -3.331409 -1.716534 -0.940392

6 -1.429741 -0.081507 0.131034

6 -0.667003 1.101955 0.176282

6 0.715386 1.044013 0.188121

6 1.388752 -0.200946 0.153903

6 0.609807 -1.377013 0.158409

6 -0.774298 -1.329395 0.138414

1 -1.174897 2.063068 0.194602

1 1.280264 1.968462 0.253152

1 1.124550 -2.332851 0.173157

1 -1.350978 -2.248327 0.168544

7 2.774046 -0.352962 0.158273

6 3.586735 0.594032 -0.213454

6 5.021436 0.441737 -0.151115

6 5.862624 1.493738 -0.574587

6 7.242809 1.377945 -0.527660

6 7.814398 0.186899 -0.049795

6 7.016741 -0.869810 0.372973

6 5.618053 -0.762221 0.329834

1 5.402700 2.408933 -0.941629

1 7.875020 2.196864 -0.855984

1 8.895747 0.086169 -0.009509

1 7.447522 -1.794828 0.742561

1 3.214475 1.545908 -0.611104

8 4.876610 -1.800092 0.741216

1 3.920230 -1.534312 0.628240

1 -3.244759 0.974682 0.128941

6 6.947659 1.075287 0.410787

6 5.550388 0.807804 0.522293

6 5.112803 -0.529071 0.131072

6 5.996658 -1.394960 -0.470390

6 7.389057 -1.087240 -0.582036

6 7.845949 0.133070 -0.120767

1 7.296838 2.031859 0.786804

1 5.639353 -2.348305 -0.853395

1 8.068832 -1.823626 -0.997093

1 8.901935 0.380794 -0.183793

8 4.695739 1.682917 0.895871

6 3.681162 -0.843404 0.259234

7 2.803679 0.101167 -0.002765

1 3.326237 -1.824941 0.560266

6 1.408466 0.022597 -0.035870

6 0.662806 1.204113 0.133685

6 -0.719737 1.173043 0.129846

6 -1.407726 -0.052720 -0.047509

6 -0.648039 -1.231031 -0.238811

6 0.733181 -1.200943 -0.234649

1 1.182205 2.146893 0.286145

1 -1.266339 2.099322 0.265511

1 -1.169089 -2.169809 -0.402889

1 1.289501 -2.114393 -0.419523

7 -2.782446 -0.163214 -0.057468

6 -3.711308 0.800227 0.089068

6 -5.076818 0.492903 0.050326

6 -6.054493 1.521416 0.207611

6 -7.396746 1.237215 0.174762

6 -7.822815 -0.108185 -0.019639

6 -6.922288 -1.134761 -0.176508

6 -5.503687 -0.900237 -0.151990

1 -5.711327 2.544156 0.355422

1 -8.132346 2.026551 0.295205

1 -8.888762 -0.324072 -0.043997

1 -7.246216 -2.160341 -0.324959

1 -3.383625 1.825558 0.240218

8 -4.660776 -1.844504 -0.296634

1 3.247742 1.046762 0.059621

1 -3.275607 -1.097900 -0.193061

E(S1)

-1031.01182586 Eh

E(S1)

-1031.00437235 Eh


21

300 400 500 600 700 8000.0

0.2

0.4

0.6

0.8

1.0

No

rma

lize

d in

ten

sity

Wavelength, nm

excitation at:

370 nm

400 nm

430 nm

Figure S1. Normalized stationary absorption (1-10-A

, where A is absorbance, dotted line) and

emission spectra of BSP in DCM upon excitation at indicated wavelength (solid lines). The

solid blue line shows the fluorescence excitation spectrum measured for 560 nm observation

wavelength and normalized to the absorption spectrum.


22

Table S1.

Time constants and their fractional amplitudes (in parentheses, normalized to 100 %) obtained

from exponential functions fits to the fs-transients (convoluted with an IRF of 210 fs) at the

indicated emission wavelengths of BSP in HEX and upon excitation at 370 nm.

Wavelength / nm 1 / fs 2 / ps 3 / ps

455 80 (100%)

535 130 (68%) 20 (32%)

550 100 (31%) 2.8 (14%) 23 (55%)

600 1.0 (23%) 21 (77%)

650 2.4 (30%) 25 (70%)

Table S2.

Time constants and their fractional amplitudes (in parentheses, normalized to 100 %) obtained

from exponential functions fits to the fs-transients (convoluted with an IRF of 220 fs) at the

indicated emission wavelengths of BSP in DCM and upon excitation at 375 nm.

Wavelength / nm 1 / fs 2 / ps 3 / ps

455 50 (100%)

490 50 (88%) 1.8 (9%) 20 (3%)

550 50 (26%) 0.7 (12 %) 20 (62%)

600 - 1.0 (15%) 19 (85%)

650 - 3.1 (23%) 20 (77%)


23

0.0 0.5 1.0 1.5 2.00.0

0.2

0.4

0.6

0.8

1.0

(A)

No

rma

lize

d in

ten

sity

Time, ps

0 10 20 30 40 500.0

0.2

0.4

0.6

0.8

1.0

(B)

No

rma

lize

d in

ten

sity

Time, ps

HEX at 415 nm

455 nm

535 nm

550 nm

600 nm

Figure S2. Femtosecond (fs) emission transients of BSP in HEX on shorter (A) and longer (B)

time scale at the indicated, representative wavelengths of observation, and upon excitation at

370 nm. The solid lines are from the best fit (see Table S1), and the dotted one is of IRF

(FWHM=210 fs) measured at the Raman emission at 415 nm.


24

0 1 2 30.0

0.2

0.4

0.6

0.8

1.0

No

rma

lize

d in

ten

sity

Time, ps

455nm, 490nm

550nm, 600nm

650nm,

DCM at 422 nm

(A)

0 5 10 15 20 25 30 35 40 45 500.0

0.2

0.4

0.6

0.8

1.0

No

rma

lize

d in

ten

sity

Time, ps

455nm, 490nm

550nm, 600nm

650nm,

(B)

Figure S3. Femtosecond (fs) emission transients of BSP in DCM on shorter (A) and longer

(B) time scale at the indicated wavelengths of observation, and upon excitation at 375 nm.

The solid lines are from the best fit (see Table 1), and the dotted one is of IRF (FWHM=220

fs) measured at the Raman emission at 422 nm.


25

0 1 2 3 4 50.960

0.965

0.970

0.975

0.980A

bso

rba

nce

at

37

0 n

m

Time, min

exc. 410 nm

exc. 550 nm

fit: 45 s rise-time

Figure S4. Temporal changes in the absorbance measured at 370 nm at the stationary

absorption setup after the irradiation of the BSP/HEX with 410 nm, 3 mJ nanosecond pulses

for 4 minutes at 10 Hz (open black squares). The time between the end of the irradiation and

the beginning of the kinetics measurements is about 25 s. The solid line shows the fit with 1-

exp rise and the characteristic time of 45 s. For the reference, the irradiation experiment with

the same conditions was performed, but with the excitation far away from the absorption band

of BSP (at 550 nm, open red circles), showing no changes in the absorbance.


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